Heteroatom containing perfluoroalkyl terminated neopentyl glycols and compositions therefrom

ABSTRACT

Heteroatom containing perfluoroalkyl terminated neopentyl glycols of the formulas HO[--CH 2  C(CH 2  X--E--R f ) 2  CH 2  O] 1-3  --H or HO[--CH 2  C(CH 2  X--R f ) 2  CH 2  O] 1-3  --H are prepared from halogenated neopentyl glycols or oxetanes and thiols of the formula R f  --E--SH, amines of the formula R f  --E--NH--R, alcohols of the formula R f  --E--OH or perfluoro-amides, wherein R f  is a straight or branched chain perfluoroalkyl of 1 to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms. 
     The polymeric reaction products of said fluorinated diols, and optionally other diols with isocyanates to prepare polyurethanes; with amines and isocyanates to prepare polyureas/polyuretanes; with acids or derivatives to prepare polyesters or polycarbonates are disclosed. These include polymeric, random or block urethane, and/or urea, and/or ester compositions containing the residue of at least one R f  -neopentyl glycol containing two perfluoroalkyl hetero groups. 
     These polymeric compositions provide improved thermal stability and useful low surface energy oil and water repellent coatings, and soil-release properties for textiles, glass, paper, leather and other materials.

This is a divisional of application Ser. No. 339,326 filed on Apr. 14,1989 now U.S. Pat. No. 4,946,992, which is a continuation-in-part ofSer. No. 209,743, filed June 20, 1988, now U.S. Pat. No. 4,898,981issued Feb. 6, 1990.

BACKGROUND OF THE INVENTION

This invention relates to hetero group containing perfluoroalkylterminated neopentyl glycols and their derived polymeric compositionsand use to impart oil and water repellency to textiles, glass, paper,leather, and other compositions.

Certain bis-perfluoroalkyl terminated neopentyl glycols devoid of sulfuror nitrogen heteroatoms have been described in U.S. Pat. Nos. 3,478,116and 3,578,701. However, such compounds are difficult and expensive toprepare and therefore are impractical intermediates from which to obtainuseful products. Additionally, other bis-perfluoroalkyl glycolscontaining sulfur are described in U.S. Pat. Nos. 3,935,277, 4,001,305,4,054,592, 4,099,642,and 4,046,944. These compounds are not readilyobtainable in high purity and are thermally unstable. The subjectperfluoroalkyl glycols are readily isolated in high yield and purity andare thermally stable. Another advantage of the subject glycols is thatthe pendant perfluoroalkyl chains are connected by flexible heterogroups to the remainder of the molecule thus providing more mobileperfluoroalkyl functions.

Bis-perfluoroalkyl glycols and polymeric derivatives thereof are usefulbecause they possess a low free surface energy which provides oil andwater repellency to a wide variety of substrates. Glycols containing asingle R_(f) -function are known, but do not provide these properties tothe same extent. The subject glycols may be prepared in high yield andpurity in contrast to prior art materials. Most importantly the instantglycols are thermally stable.

DETAILED DISCLOSURE

One aspect of this invention relates to a method of making such R_(f)-glycols. Another aspect of this invention relates to derived R_(f)-containing polyurethane/polyurea/or polyester-containing compositions.One embodiment of this invention relates to hydroxyl terminatedprepolymers of the R_(f) -glycol prepared from polyisocyanates, lactonesor isocyanate terminated prepolymers. If desired, R_(f) -glycols can beconverted to isocyanate terminated prepolymers to form reactivecompositions with alcohols, polyols, polyamines, R_(f) -glycols, polyolprepolymers and hydroxyl terminated R_(f) -containing prepolymers. Inanother embodiment, the R_(f) -glycols can be used to replace part orall of the hydroxyl component in a urethane composition.

Another embodiment of such polymeric compositions relates to reactivecompositions comprising aliphatic polyester segments comprised of thesubject R_(f) -neopentyl glycol reacted with dicarboxylic acids, esters,anhydrides, lactones or acid chlorides, the mole ratios being adjustedto obtain the desired hydroxy or carboxyl end group functionality. Inanother embodiment suitable functionally terminated polyester polyolsare described in Encyclopedia of Polymer Science and Technology,Interscience Pub., 11 (1969), p. 513; these can be linked with the R_(f)-diol to form the polyesters of this invention. Alternately, the R_(f)-diol can be coreacted with the polyester precursor reagents, e.g.,dicarboxylic acid and aliphatic diol, under esterification conditions.The fluorochemical polyesters can also be derived from isocyanatecontaining prepolymers, e.g. isocyanate end-capped R_(f) -glycol andhydroxy terminated polyester segments as described herein.

In another embodiment, the polymers are more appropriately defined asblock polymers and contain 15-70% of a fluorochemical block connected to30-85% by weight of a hydrophilic block. These blocks are mostpreferably connected by urea linkages in the final product condensateand are useful as coatings on textiles, glass, linoleum, leather, wood,tile, metals, plastics, and various materials. They are of particularuse on textile materials as soil release agents, showing increaseddurability as compared to urethane-connected condensation blockpolymers.

This invention most generally relates to novel heteroatom containingperfluoroalkyl terminated neopentyl glycols and derived polymericurethane, and/or urea and/or ester linked compositions containing saidR_(f) -glycols.

Another aspect of this invention relates to a substrate containing 0.01to 10% by weight of a fluorine-containing urethane and/or urea, and/orester composition, at least part of said fluorine being provided by oneor more units derived from the heteroatom containing R_(f) -neopentylglycol.

The novel heteroatom containing R_(f) -neopentyl glycols have thegeneral formula I or II ##STR1## wherein

R_(f) is a straight or branched chain perfluoroalkyl of 1 to 18 carbonatoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6carbon atoms,

E is branched or straight chain alkylene of 1 to 10 carbon atoms or saidalkylene interrupted by one to three groups selected from the groupconsisting of --NR--, --O--, --S--,--SO₂ 13 , --COO--, --OOC--,--CONR--,--NRCO--, --SO₂ NR--, and --NRSO₂ --, or terminated at theR_(f) end with --CONR-- or --SO₂ NR--, where R_(f) is attached to thecarbon or sulfur atom, and for formula I, X is --S--, --O--, --SO₂ --,or --NR--, and for formula II, X is --CONR-- or --SO₂ NR--, where R_(f)is attached to the carbon or sulfur atom, and where R is independentlyhydrogen, alkyl of 1 to 6 carbon atoms or hydroxyalkyl of 2 to 6 carbonatoms, and m is 1, 2 or 3.

It is understood that the R_(f) group usually represents a mixture ofperfluoroalkyl moieties. When the R_(f) group is identified as having acertain number of carbon atoms, said R_(f) group also usuallyconcomitantly contains a small fraction of perfluoroalkyl groups with alower number of carbon atoms and a small fraction of perfluoroalkylgroups with a higher number of carbon atoms.

Preferably the instant compounds of formula I are those where R_(f) isperfluoroalkyl of 2 to 12 carbon atoms or perfluoroalkyl of 2 to 6carbon atoms substituted by perfluoroalkoxy of 2 to 6 carbon atoms, E isalkylene of 2 to 6 carbon atoms, --CONHCH₂ CH₂ --, --CH₂ CH₂ N(CH₃)CH₂CH₂ --, --CH₂ CH₂ SO₂ NHCH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, or --SO₂NHCH₂ CH₂ --, X is --S--, --SO₂ -- or --O--, and m is 1 or 2.

Most preferred are those compounds where R_(f) is perfluoroalkyl of 6 to12 carbon atoms, E is ethylene, m=1, and X is S, i.e.,

    (R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2).sub.2 C(CH.sub.2 OH).sub.2

In another group of most preferred compounds R_(f) is perfluoroalkyl of6 to 12 carbon atoms, E is ethylene, m=2, and X is S ##STR2##

The novel R_(f) -glycols can be obtained directly by the reaction of aperfluoroalkyl thiol of formula R_(f) -E-SH or a perfluoroalkyl amine offormula R_(f) -E-NR₂ with a dihalogenated pentaerythritol of formula

    (YCH.sub.2).sub.2 C(CH.sub.2 OH).sub.2,

or a dipentaerythritol of formula

    HO[CH.sub.2 C(CH.sub.2 Y).sub.2 CH.sub.2 O].sub.2 H,

where y is Cl, Br, or I.

In one preferred embodiment, the neopentyl derivative isdibromopentaerythritol and has the formula (BrCH₂)₂ C(CH₂ OH)₂. Inanother preferred embodiment tetrabromodipentaerythritol HO[CH₂ C(CH₂Br)₂ CH₂ O]₂ H, is used. These intermediates are commercially availablein high purity; dichloro and iodo neopentyl glycols have also beenreported.

The synthesis of R_(f) -diols proceeds by the nucleophilic substitutionof a perfluoroalkyl substituted thiolate or amine for halide. Thereaction may be conducted in an aqueous system using phase transfercatalysis, but work-up of such an aqueous product is difficult due totroublesome emulsions. The improved process of this invention involvesthe combination of:

a. an aprotic solvent, such as N-methylpyrrolidone,N,N-dimethylformamide, dimethyl sulfoxide, or the like, or ketones, suchas acetone, methyl alkyl ketones, or dialkyl ketones. Chlorinatedsolvents and esters generally give poor conversions and are unsuitable;

b. moderate reaction temperatures, on the order of 50° to about 120° C.;and

c. a stoichiometric quantity of an anhydrous alkaline earth carbonate,preferably potassium carbonate, in the ratio of 1 mole of carbonate permole of halide to be displaced; and

d. in the case of the amines, tertiary amine catalysis is useful asexemplified by triethylamine, tributylamine, dimethylaminopyridine, orpiperidine.

e. in the case of the oxygenated ethers or sulfonamides, Crown ethercatalysis is useful as exemplified by 12-Crown-4, 15-Crown-5, and18-Crown-6.

The reaction temperature, and choice of solvent are mutually dependent.A reaction temperature in the range of 50°-140° C. is one wherein theformation of undesirable by-products is minimized and wherein thereaction products are stable.

Conditions are adjusted in order to achieve a reasonable rate ofreaction at the chosen temperature.

Alternately, the subject diols are obtained indirectly by the reactionof 3,3-bis-(halomethyl)oxetane of formula ##STR3## where Y is Cl, Br, orI, with a perfluoroalkanol of formula R_(f) --E--OH or aperfluoroalkylsulfonamide of formula R_(f) --SO₂ NHR, followed byhydrolysis of the oxetane linkage to diol.

In the synthesis of the R_(f) -glycols a number of by-products may bepresent. These are derived in part from trace impurities present in thediol and in part as reaction intermediates. When the starting thiol isR_(f) --CH₂ CH₂ SH and dibromoneopentyl glycol is used these by-productsinclude ##STR4##

    R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 C(CH.sub.2 OH).sub.3 and

    R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2 C(CH.sub.2 OH).sub.2 CH.sub.2 Br

Such intermediates and the oxetane formation are consistent with thegeneral reaction conditions.

It should be noted that the ready oxidation of thiols to disulfidesrequires that the chemistry be conducted in an inert atmosphere.

The subject diols can also be made by first reacting the bromodiolintermediates with a functional thiol or amine, e.g. HSCH₂ CH═CH₂, HSCH₂COOH or NH₂ CH₂ CH═CH₂. The resultant sulfide or amine can then bereacted with the R_(f) -containing moiety by a suitable chemistry whichdoes not involve the pendant hydroxyl groups.

For example, ##STR5##

An alternate synthesis has also been demonstrated. Dibromoneopentylglycol can be converted to 2,6-dioxaspiro-[ 3.3]heptane as reported byAbdun-Nur and Issidorides in J. Org. Chem. 27, 67-69 (1962), and thisintermediate converted to R_(f) -diol. ##STR6##

This synthetic approach is less favorable since the volatilespiro-oxetane must first be isolated. Attack by the thiolate nucleophileoccurs readily on the spiro compound, but the resultant oxetane reactswith difficulty. The process involves the combination of:

a. a solvent in which the spiro-oxetane is soluble, preferablyn-butanol;

b. reaction temperatures of 55°-150° C. The reaction temperature is keptlow initially to avoid volatilization of the oxetane and is increased asthe reaction proceeds; and

c. a basic catalyst, e.g. sodium methoxide or potassium t-butoxide.

The reaction temperature and solvent are mutually dependent. Underappropriate conditions with n-butanol, at 55° C./4.5 hours (1/2 thiolcharge) and then 125° C./16.5 hours (remainder of thiol charge), theproduct formed assayed 17% monoadduct, 78% diadduct.

The subject sulfido-linked diols can be readily oxidized to thecorresponding bis-sulfone diols by peracetic acid (H₂ O₂ /acetic acid)or by other conventional oxidants which selectively oxidize sulfides inthe presence of alcohol functions. With peracetic acid, temperatures of30°-100° C. are appropriate depending on the amount of excess oxidizingagent to ensure that the intermediate sulfoxides are completelyoxidized.

Perfluoroalkyl thiols useful herein are well documented in the priorart. For example, thiols of the formula R_(f) -E-SH have been describedin a number of U.S. Pat. Nos. including 3,655,732 and 4,584,143.

Thus, U.S. Pat. No. 3,655,732 discloses mercaptans of formula

    R.sub.f -E-SH

where

E is alkylene of 1 to 16 carbon atoms and R_(f) is perfluoroalkyl, andteaches that halides of formula R_(f) -E-Halide are well-known; reactionof R_(f) I with ethylene under free-radical conditions gives R_(f) (CH₂CH₂)_(a) I while reaction of R_(f) CH₂ I with ethylene gives R_(f) CH₂(CH₂ CH₂)_(a) I as is further taught in U.S. Pat. Nos. 3,088,849;3,145,222; 2,965,659 and 2,972,638.

U.S. Pat. No. 3,655,732 further discloses compounds of formula R_(f)-R'-Y-R"-SH where

R' and R" are alkylene of 1 to 16 carbon atoms, with the sum of thecarbon atoms of R' and R" being no greater than 25; R_(f) isperfluoroalkyl of 4 through 14 carbon atoms and Y is --S-- or--NR'"--where R'" is hydrogen or alkyl of 1 through 4 carbon atoms.

U.S. Pat. No. 3,544,663 teaches that the mercaptan

    R.sub.f CH.sub.2 CH.sub.2 SH

where

R_(f) is perfluoroalkyl of 5 to 13 carbon atoms, can be prepared byreacting the perfluoroalkyl alkylene iodide with thiourea or by addingH₂ S to a perfluoroalkyl substituted ethylene (R_(f) --CH═CH₂), which inturn can be prepared by dehydrohalogenation of the halide R_(f) --CH₂CH₂ --halide.

The reaction of the iodide R_(f) -E-I with thiourea followed byhydrolysis to obtain the mercaptan R_(f) -E-SH is the preferredsynthetic route. The reaction is applicable to both linear and branchedchain iodides.

Particularly preferred herein are the thiols of formula

    R.sub.f CH.sub.2 CH.sub.2 SH

where

R_(f) is perfluoroalkyl of 6 to 12 carbon atoms. These R_(f) -thiols canbe prepared from R_(f) CH₂ CH₂ I and thiourea in very high yield.

Perfluoroalkylamines useful herein are well documented in the prior art.For example, C₆ F₁₃ CH₂ CH₂ NH₂ has been described in Japan Kokai77/118,406. R_(f) CH₂ NH₂ wherein R_(f) is CF₃ through CF₃ (CF₂)₁₁ aredescribed in British Patent No. 717,232 (1954).

Further R_(f) SO₂ NR(CH₂)_(n) NR(CH₂)₃ NH₂ and R_(f) CH₂ CH₂ SO₂NH(CH₂)_(n) NR₂ are described in G.B. 1,106,641 and U.S. Pat. No.3,838,165 respectively; R_(f) CONH(CH₂)_(n) NH₂ in Jap. Kokai 52/14767.

Perfluoroalkanols useful herein are well documented in the prior art andmany are commercially available. They have the general formula R_(f)-E-OH and include:

    C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)C.sub.2 H.sub.4 OH

    C.sub.8 F.sub.17 C.sub.2 H.sub.4 OH

    C.sub.7 F.sub.15 CH.sub.2 OH

    C.sub.7 F.sub.15 CON(C.sub.2 H.sub.5)C.sub.2 H.sub.4 OH

    C.sub.8 F.sub.17 C.sub.2 H.sub.4 SC.sub.2 H.sub.4 OH

    (CF.sub.3).sub.2 CF(CF.sub.2).sub.8 C.sub.2 H.sub.4 OH

    (CF.sub.3).sub.2 CFOC.sub.2 F.sub.4 C.sub.2 H.sub.4 OH

    C.sub.8 F.sub.17 C.sub.2 H.sub.4 SO.sub.2 N(CH.sub.3)C.sub.4 H.sub.8 OH

    C.sub.8 F.sub.17 CH.sub.2 OH

    CF.sub.3 CH.sub.2 OH

    C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SO.sub.2 NHCH.sub.2 CH.sub.2 OH

Perfluoroalkylsulfonamides useful herein are well documented in theprior art such as in U.S. Pat. No. 2,915,554 and include compounds ofthe general structure R_(f) -SO₂ NHR, such as

    C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)OH

    C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)H

    C.sub.8 F.sub.17 SO.sub.2 N(i-C.sub.3 H.sub.7)H

    C.sub.10 F.sub.21 SO.sub.2 N(C.sub.2 H.sub.5)H

    C.sub.10 F.sub.21 SO.sub.2 NH.sub.2

The diols, can be used directly or indirectly to make a variety ofcondensation products such as polyesters, polyureas, polycarbonates,polyurethanes and the like. Polyurethanes are particularly preferred.

As used herein the term "urethane composition" means compounds andcompositions which contain the characteristic ##STR7## linkage and atleast one R_(f) -containing group of formula ##STR8## where

R_(f), X and E are as previously described, and a similar structure canbe drawn for a structure (II) type diol.

Preferred urethane compositions include those where R_(f), and E havethe configurations previously described as being preferred and X is S,SO₂ or O.

The R_(f) -glycols can be used to make a wide variety of urethaneintermediate and end products including hydroxyl andisocyanate-terminated prepolymers, low molecular weight urethanecompositions useful to render plastics soil repellent, and highmolecular weight compositions useful as elastomers, foams, paints andvarnishes, and textile treating compositions. It is also possible tomodify these R_(f) -containing urethane compositions so that they arewater soluble or self-emulsifiable, a property that is particularlyuseful in connection with the textile treating compositions. Blockpolymer compositions of the R_(f) containing diols and hydrophilicblocks have special utility in the textile industry as soil-releaseagents.

These compositions have extremely low free surface energies andtherefore, possess oil and water repellent properties, as well as moldrelease and other properties associated with low free surface energy. Itshould be noted that the compositions of this invention arecharacterized by the presence of two perfluoroalkylhetero groups inclose proximity, a characteristic which provides improved oil and waterrepellent properties over the fluorinated compositions of the prior art.Further the two perfluoroalkylthio groups are connected via a neopentylmoiety which does not permit the thermal elimination of mercaptan bybeta-elimination. Hence, these R_(f) -diols and derivatives haveenhanced thermal stability. The beta-elimination reaction of prior artsulfur containing R_(f) -diols as disclosed in U.S. Pat. No. 4,097,642is shown in the following equation. ##STR9##

Using the R_(f) -compounds and compositions described herein, it ispossible to manufacture molds that display the excellent releaseproperties characteristic of silicone polymers. It is also possible toprepare polymeric compositions with enhanced thermal stability.

ELASTOMERS

Polyurethane elastomers generally have remarkable resistance to mostsolvents including gasoline, aliphatic hydrocarbons and, to some degree,aromatic hydrocarbons. They also exhibit excellent abrasion resistance.By inclusion of the R_(f) -glycol in an elastomer formulation, it ispossible to increase the solvent resistance of urethane elastomers. Theelastomers generally involve the reaction product of a diisocyanate, alinear long chain diol and a low molecular weight chain extender such asa glycol, diamine or polyol. Today, elastomers are generally prepared bya prepolymer technique whereby a diisocyanate is reacted with ahydroxyl-terminated polyester or polyether to form anisocyanato-terminated prepolymer. This prepolymer is then furtherreacted (chain extended) with a glycol, diamine or polyfunctional polyol(e.g. trimethylolpropane). Following the chain extension step, theliquid material solidifies and is removed from a mold and cured atelevated temperatures.

Urethane foams are usually prepared from diisocyanates andhydroxyl-terminated polyethers or polyesters. Linear or slightlybranched polymers are used to provide flexible foams while more highlybranched polymers produce rigid foams. Foaming is often accomplished byincluding water in the system, the reaction between isocyanate and waterproviding carbon dioxide for foaming. For rigid foams a low-boilingliquid such as trichlorofluoromethane has been used as a blowing agent.

Appropriate selection of catalysts, stabilizers, surfactants and otheradditives controls the foam formation, cell size and type, density, cureand the like. By incorporating the R_(f) -glycol into urethane foams,especially molded foams, it is possible to achieve improved mold releaseproperties in rigid, semi-rigid and flexible foams. It is also possibleto improve the water and solvent resistance of foams used as insulation.

COATINGS

Incorporation of the R_(f) -glycols into polyurethane coatings such aspaints and varnishes improves the water and solvent resistance thereof.Widely used systems include the two-component coatings wherein anon-volatile isocyanate derived from the reaction of tolylenediisocyanate with a polyol, such as trimethylolpropane, is reacted witha polyfunctional polyester. Another system in use involves theone-component polyurethane coatings which are based on stableisocyanate-terminated prepolymers obtained from a diisocyanate such astolylene diisocyanate and a polyfunctional polyether. Such coatings dryby the reaction of the free isocyanate groups with water or atmosphericmoisture. The reaction proceeds through the unstable carbamic acid, withCO₂ being eliminated, to give primary amine groups which further reactwith isocyanate groups to form ureas.

Treatment of a textile with a fluorine-containing composition, notably afluorine-containing polymer, provides oil and water-repellentcharacteristics thereto. Such compositions containing the residue of theR_(f) -glycol display improved oil and water repellence on textilesubstrates.

In higher molecular weight urethane compositions, linear polymer,obtained by reacting an R_(f) -glycol with an organic diisocyanate,having recurring structural units of formula ##STR10## where

R_(f), E and X are as previously defined, where m is 1 or 2, and asimilar structure can be drawn for a type (II) diol, and A is a divalentorganic radical, preferably alkylene of 2 to 16 carbon atoms,cycloalkylene of 6 to 15 carbon atoms, unsubstituted or substitutedphenylene or naphthylene or unsubstituted or substituted biphenylene orbisphenylene. The polymers are useful as plastics, fibers, coatings andthe like.

SOIL RELEASE AGENTS

The treatment or modification of fabrics to improve their properties isroutine practice in the textile industry. However, resin-treated durablepress garments are difficult to clean because they are prone to soilretention. Investigation of this phenomenon showed that resin treatedcotton as well as the synthetic fibers are oleophilic and accordingly,dirt, particularly oily stains, clings tenaciously to the fabricsubstrate and is extremely difficult to remove under normal home washingconditions.

In an effort to overcome the soil removal resistance of resin-treatedfabrics, artisans have commonly treated such fabrics with a hydrophiliccolloid such as carboxymethyl cellulose and synthetic polymers such aspolyacrylic acid and copolymers of acrylic acid with lower alkylacrylates and methacrylates. These materials, which are referred to assoil release agents, apparently coat the textile fibers with ahydrophilic film which allows the fibers to be wet effectively bydetergent solutions so that the soils are readily removed by laundering.

The combination of oleophobic fluorinated groups and hydrophilicpoly(ethyleneoxide) containing groups in one polymer to achieve therelease of oil stains from textiles has been described in U.S. Pat. Nos.3,728,151 and 3,758,447. The advantage of fluorinated soil releaseagents over non-fluorinated ones stems from their oleophobic nature,which (a) prevents the wicking of oil stains into the fabrics and (b)facilitates the lifting off of the staining material from the fabricwhen it is washed.

It has also been reported that certain segmented (block)polyurethane/polyureas are useful soil-release agents--see U.S. Pat. No.4,046,944.

The oleophobic blocks are comprise of fluorinated aliphatic groups heldtogether in segments directly or through linkages made up of variouscombinations of functional groups and/or hydrocarbon chains. Thepreferred hydrophilic segments are based on polyoxyalkylene glycols orend-capped derivatives thereof. The molecular weight of the glycols mayrange from about 150 to 10,000 or more and may be repeated from 1 to 500or more times.

A preferred embodiment of this invention is that a great increase inperformance, especially in durability of fluorochemical textilefinishes, can be achieved by use of polymer condensates, wherein theoleophobic and hydrophilic blocks are preferably connected by urealinkages rather than urethane linkages. A block polymer comprisingoleophobic fluorinated blocks and hydrophilic poly(ethyleneoxide) blocksconnected by urea linkages and having increased durability when appliedto materials such as textiles is thus provided.

The fluorinated condensation polymers are made up of a combination ofBlocks I and II: ##STR11## In these structures:

R_(f) is derived from the subject R_(f) -glycols

R₄ is hydrogen or methyl,

A is the organic divalent radical of a diisocyanate,

k is 8-100

t and p are integers of 1 to 5

X is S, SO₂, O, or NR.

and a similar Block (I) can be described for type (II) diols.

It will be noted that the invention condensation polymers, being made upof Blocks I and II, are of the pattern: ##STR12##

The molecular weight of Blocks I and II will vary, depending on thesubstituents and the number of repeating units in each. However, theadvantages combination of Blocks I and II can be achieved by the use ofmonomer or prepolymer reactants so as to give 15-70% Block I to 30% to85% Block II in the final polymer.

The segmented perfluoroalkyl/hydrophilic polymers are useful onsubstrates as coatings, which will (1) prevent, or at least reduce,soiling and (2) release soil when washed with water. They are thereforeuseful as ingredients in floor polishes, furniture waxers, windowwashing fluids, and so on; their most important application is as asoil-release finish on textiles, especially polyester/cotton textiles.Generally, they are useful as coatings on glass, ceramics, masonry,wood, plastics, textiles, leather and metals, or as additive ingredientsin such coatings.

Most urethane compositions that are used commercially to any greatextent are copolymers that contain only a relatively small number ofurethane linkages. These copolymers are prepared from a variety ofsegments, typically based on polyethers and polyesters and can have amolecular weight of from 200 to 10,000, generally from about 200 toabout 4,000. By the inclusion of an appropriate amount of R_(f) -glycolin the starting materials, it is possible to prepare prepolymers that,when incorporated as part of a urethane composition favorably affect theproperties thereof. It is similarly possible to incorporate a desiredamount of R_(f) -glycol into the reaction mixture of a conventionalprepolymer and an isocyanate so as to obtain conventional urethanecompositions containing the divalent residue of the R_(f) -glycol. Inthe same way, there can be added an R_(f) -containing prepolymertogether with or instead of the R_(f) -glycol.

The R_(f) -containing prepolymers can be hydroxy-terminated orisocyanate-terminated and, as indicated, can have a molecular weight ashigh as 10,000 although a molecular weight of 200 to about 4,000 is moreusual.

Hydroxy-terminated prepolymers can be prepared by reacting an excess ofa polyhydroxy component with a polyfunctional hydroxy-reactive componentsuch as a polyisocyanate; an isocyanate-terminated prepolymer; apolybasic carboxylic acid, anhydride or acrylyl halide; phosgene; or abischloroformate.

The polyhydroxy component can be a polyol, an R_(f) -glycol, apolyether, a polyester, an R_(f) -containing polyether, an R_(f)-containing polyester or mixture thereof.

The polyols are well-known in the urethane art and include:

Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1-5-pentanediol,1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, di-, tri-, tetra- andpentaethylene glycol, bis(4-hydroxybutyl) ether, bis(2-hydroxyethyl)thioether, bis(4-hydroxybutyl) thioether,1,4-bis(3-hydroxypropyl)benzene, glycerol, trimethylolpropane,1,2,6-hexanetriol, sorbitol, mannitol, pentaerythritol,2-ethyl-1,3-butylene glycol, octamethylene glycol,2-ethyl-1,3-hexanediol, dodecamethylene glycol, tetradecamethyleneglycol, hexadecamethylene glycol, octadecamethylene glycol.

The polyol can also contain cycloaliphatic groups, e.g.1,4-cyclohexane-diol, 1,4-bis(hydroxymethyl)cyclohexane,4,4'-dihydroxyl-1,1'-dicyclohexyl and the like. If desired, mixtures ofpolyols can be used.

Polyols in addition to those described above, that are consideredespecially useful, are those containing tertiary nitrogen atoms whichcan be quaternized with acids, thereby converting a water-insolubleurethane composition into one that is water soluble or emulsifiable.Generally, an isocyanate-terminated prepolymer having a molecular weightof 200 to 10,000 preferably 400 to 4,000, is reacted with a difunctionaltertiary amine to provide a segmented polymer containing tertiarynitrogen atoms. The nitrogen atoms can be quaternized, for example, byalkylation with methyl chloride or dimethyl sulfate to yield acomposition that is polar media yields a dispersion in water. Thepolyammonium polyurethane compositions are obtained even more readily byneutralization of the basic polyurethane composition in a polar organicsolvent such as acetone, methyl ethyl ketone, tetrahydrofuran, with astrong (HCl) or preferably weak (pk>4) acid such as the C₂ -C₉ alkanoicacids. Acetic acid is especially preferred because the acetic acidevaporates with the water on drying to leave the water-insolublehydrophobic starting polyurethane composition.

The neutralized polyurethane composition in a polar solventspontaneously forms a dispersion when water is added. The solvent canthereafter be distilled off to give a solvent-free latex whosefilm-forming qualities are comparable to those of the organic solution.

In a convenient mode of preparing the water-dispersible basicpolyurethane compositions, a polyester or polyether diol is reacted in anon-reactive polar solvent, such as acetone, methyl ethyl ketone,tetrahydrofuran and the like, with an excess of a diisocyanate such astolylene diisocyanate or, preferably an aliphatic diisocyanate whichtends to give non-yellowing urethanes such as dimer acid deriveddiisocyanate (DDI, commercially available from Quaker Oats Company) oranother diisocyanate which is described herein as providingnon-yellowing urethanes, and the prepolymer partially chain extendedwith an alkyl diethanolamine to yield a urethane composition containingtertiary amino groups. The urethane composition can then be acidifiedwith a solution of aqueous weak acid (pk>4) such as acetic acid; theconcentration of acid is not critical. An emulsion immediately formswhen this composition is added to water.

The polyurethane compositions can contain from as little as 5 to 800milliequivalents of ammonium groups per 100 grams of polyurethanecomposition, preferably from about 50 to about 500 milliequivalents ofammonium groups per 100 grams.

Some useful polyols containing tertiary nitrogen atoms can berepresented by the formula: ##STR13## where

R₁₀ and R₁₁ are alkyl of 2 to 4 carbon atoms or a group of formula##STR14## where

R₁₃ and R₁₄ are alkyl of 2 to 4 carbon atoms

R₁₂ is alkyl of 1 to 18 carbon atoms, cyclohexyl, tolyl, xylyl,naphthyl, or pyridyl.

Useful polyols that contain tertiary nitrogen atoms include thealkoxylated aliphatic, cycloaliphatic aromatic and heterocyclic primaryamines:

N-methyl-diethanolamine, N-butyl-diethanolamine, N-oleyldiethanolamine,N-cyclohexyl-diethanolamine, N-methyldiisopropanolamine,N-cyclohexyl-diisopropanolamine, N,N-dihydroxyethylaniline,N,N-dihydroxyethyl-m-toluidine, N,N-dihydroxyethyl-p-toluidine,N,N-dihydroxypropyl-naphthylamine, N,N-tetrahydroxyethyl-aminopyridine,polyethoxylated butyldiethanolamine, polypropoxylatedmethyldiethanolamine (molecular wt. 1000), and polypropoxylatedmethyldiethanolamine (molecular wt. 2000); also useful are polyesterswith tertiary amino groups,tri-2-hydroxypropyl-(1)-amine,N,N-di-n-(2:3-dihydroxypropyl)-amine,N,N'-bis-hydroxypropylethylenediamine,N,N'-dimethyl-N,N'-bis-(hydroxyethyl)-ethylenediamine,11-stearyldiethanolamine.

The R_(f) -glycols can be incorporated in the water-dispersible urethanecompositions in an amount sufficient to provide the desired improvementin the surface properties of the polyurethane composition.

Useful polyethers are well-known and widely employed in urethanetechnology.

The polyethers are generally prepared commercially from lower alkyleneoxides e.g. ethylene, propylene and butylene oxide and di- orpolyfunctional alcohols. They have a molecular weight of from 400 to5000. A list of commercially available polyethers, trade names,molecular weight range and suppliers can be found in Volume 11,Polyurethane, page 511, Encyclopedia of Polymer Science and Technology,John Wiley and Sons, Inc., 1969.

Hydroxy-terminated polyesters can be prepared from a polybasic acid,anhydride or aryl halide and a polyol, as described above and/or anR_(f) -glycol.

Useful dicarboxylic acids are those derived from a saturated aliphaticor cycloaliphatic dicarboxylic acid of 2 to 36 carbon atoms or anaromatic dicarboxylic acid of 8 to 18 carbon atoms, e.g. compounds offormula L(COOH)₂ where L is preferably alkylene of 0-16 carbon atoms orarylene of 6 to 16 carbon atoms. Such acids include oxalic, malonic,succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic,brassylic, octadecanedioic, dimer acid, 1,4-cyclohexanedicarboxylic,4,4'-dicyclohexyl-1,1'-dicarboxylic, phthalic, isophthalic,terephthalic, methylphthalic, chlorophthalic,diphenyl-2,2'-dicarboxylic, diphenyl-4,4'-dicarboxylic, 1,4-naphthalenedicarboxylic, diphenylmethane-2,2'-dicarboxylic,diphenylmethane-3,3'-dicarboxylic, diphenylmethane-4,4'-dicarboxylicacid and the like.

Adipic acid and phthalic anhydride are the most common acid andanhydride. Of the polyols, the most commonly used include ethyleneglycol, propylene glycol, 1,2-, 1,3- and 1,4-butylene glycol,1,6-hexylene glycol, trimethylolpropane, glycerol, 1,2,6-hexanetriol anddiethylene glycol.

Useful hydroxyl-terminated polyesters can also be derived from naturalcaster oil and glycerol, from caprolactones and ethylene glycol. Suchhydroxy-terminated polyesters have hydroxyl numbers ranging from 40 to500 and very low acid numbers ranging from 0 to 2.

Hydroxyl-terminated polycarbonates can be obtained by reacting an excessof a polyol with phosgene. Hydroxyl terminated polyether carbonates arealso available and suitable for this invention.

Hydroxy-terminated polybutadienes, or butadiene styrenes andbutadiene-acrylonitriles are useful herein, as are hydroxyl containinggraft polymers of the polyether polyacrylonitrile type.

Any convenient isocyanate can be used to react with the R_(f) -glycol orR_(f) -containing hydroxy-terminated prepolymer. Myriads of usefulisocyanates are well-known in the art. Thus, one can use aliphatic oraromatic isocyanates, diisocyanates, triisocyanates and polyisocyanates.

Useful aromatic diisocyanates can be represented by the formula

    A(NCO).sub.2

where

A is phenylene that is unsubstituted or substituted by one or two alkylsof 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chloro, bromo andnitro, naphthylene that is unsubstituted or substituted by one or two ofalkyl of 1 to 4 carbon atoms, chloro, bromo and nitro or where

A is a group of formula ##STR15## where

D is a direct bond, oxygen, methylene or ethylene and

a, a', a" and a'" each independently are hydrogen, alkyl of 1 to 4carbon atoms, alkoxy of 1 to 4 carbon atoms, chloro or bromo.

Aromatic triisocyanates can be represented by the formula

    G(NCO).sub.3

where

G is the benzene or toluene group.

Aromatic di- and triisocyanates as described above include

Tolylene diisocyanate (TDI) (all isomers), 4,4'-diphenylmethanediisocyanate (MDI), tolidine diisocyanate, dianisidine diisocyanate,m-xylylene diisocyanate, p-phenylene diisocyanate, m-phenylenediisocyanate, 1-chloro-2,4-phenylene diisocyanate,3,3'-dimethyl-4,4'-bisphenylene diisocyanate,4,4'-bis(2-methylisocyanatophenyl)methane, 4,4'-bisphenylenediisocyanate, 4,4'-bis(2-methoxyisocyanatophenyl)methane,1-nitro-phenyl- 3,5-diisocyanate, 4,4'-diisocyanatodiphenyl ether,3,3'-dichloro-4,4'-diisocyanatodiphenyl ether,3,3'-dichloro,4,4,'-diisocyanatodiphenyl- methane,4,4'-diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl,2,2'-dimethyl-4,4'-diisocyanatodiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanatodiphenyl, 3,3'dichloro-4,4'-diisocyanatodiphenylbenzene-1,2,4-triisocyanate, benzene-1,3,5-triisocyanate,benzene-1,2,3-triisocyanate, toluene 2,4,6-triisocyanate, toluene2,3,4-triisocyanate, 1,2-naphthalene diisocyanate,4-chloro-1,2-naphthalene diisocyanate, 4-methyl-1,2-naphthalenediisocyanate, 1,5-naphthalene diisocyanate, 1,6-naphthalenediisocyanate, 1,7-naphthalene diisocyanate, 1,8-naphthalenediisocyanate, 4-chloro-1,8-naphthalene diisocyanate, 2,3-naphthalenediisocyanate, 2,7-naphthalene diisocyanate, 1,8-dinitro-2,7-naphthalenediisocyanate, 1-methyl-2,4-naphthalene diisocyanate,1-methyl-5,7-naphthalene diisocyanate, 6-methyl-1,3-naphthalenediisocyanate, 7-methyl-1,3-naphthalene diisocyanate, polymethylenepolyphenyl isocyanate and coproducts of hexamethylene diisocyanate andtolylene diisocyanate.

Useful aliphatic diisocyanates include those of general formula

    A(NCO).sub.2

where

A is straight or branched chain alkylene of 2 to 16 carbon atoms,optionally contining halides or cycloaliphatic functions.

Useful aliphatic or cycloaliphatic polyisocyanates include--1,2-ethanediisocyanate, 1,3-propane diisocyanate, 1,4-butane diisocyanate,2-chloropropane-1,3-diisocyanate, pentamethylene diisocyanate,propylene-1,2-diisocyanate, 1,6-hexane diisocyanate, 1,8-octanediisocyanate, 1,10-decane diisocyanate, 1,12-dodecane diisocyanate,1,16-hexadecane diisocyanate and other aliphatic diisocyanates such as1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexanetriisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate).

Additionally, the following diisocyanates are particularly preferredbecause urethane compositions made therefrom tend to be non-yellowing:

1,6-hexamethylene diisocyanate (HDI), 2,2,4- and2,4,4-trimethylhexamethylene diisocyanate (TMDI), dimer acid deriveddiisocyanate (DDI) obtained from dimerized fatty acids, such as linoleicacid 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI),isophorone diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyldiisocyanate, lysine methyl ester diisocyanate (LDIM),bis(2-isocyanatoethyl) fumarate (FDI),bis(2-isocyanatoethyl) carbonate,m-tetramethylxylylene diisocyanate (TMXDI), where

D is the residue of a diisocyanate as described above; additionalpolyisocyanates include polymethylene polyphenylisocyanate (PAPI) andtris-(isocyanatophenyl) thiophosphate (Desmodur).

Additional isocyanate components can be prepared by reacting an excessof a diisocyanate as described above with a suitable hydroxyl component,such as a polyol as described above or an R_(f) -glycol as describedherein, or combination thereof, to obtain an isocyanate-terminatedprepolymer.

In addition to the polyisocyanate, useful urethane compositions can beobtained from the aliphatic and aromatic monoisocyanates. The lowmolecular weight urethane compositions obtained by reacting an R_(f)-glycol with a monoisocyanate are useful to impart soil and mold-releaseproperties to a variety of natural and synthetic polymers.

Some useful aromatic monoisocyanates include--2-fluorophenyl isocyanate,3-fluorophenyl isocyanate, 4-fluorophenyl isocyanate,m-fluorosulfonylphenyl isocyanate, trans-2-phenylcyclopropyl isocyanate,m-tolyl isocyanate, p-tolyl isocyanate, 1,1,1-trifluoro-o-tolylisocyanate, 1,1,1-trifluoro-m-tolyl isocyanate, p-bromophenylisocyanate, 2,5-dimethylphenyl isocyanate, o-ethoxyphenyl isocyanate,p-ethoxyphenyl isocyanate, o-methoxyphenyl isocyanate, m-methoxyphenylisocyanate, p-methoxyphenyl isocyanate, 1-naphthyl isocyanate,o-nitrophenyl isocyanate, m-nitrophenyl isocyanate, p-nitrophenylisocyanate, p-phenylazophenyl isocyanate, o-tolyl isocyanate.

Useful aliphatic or cycloaliphatic monoisocyanates include such alkylisocyanates of 1 to 16 carbon atoms as methyl isocyanate, ethylisocyanate, n-propyl isocyanate, n-butyl isocyanate, t-butyl isocyanate,hexyl isocyanate, octyl isocyanate, 2-dodecyl isocyanate, octadecylisocyanate, hexadecyl isocyanate and mixtures thereof, as well ascyclohexyl isocyanate.

m-Isopropenyldimethyl benzyl isocyanato (TMI) isocyanate-terminatedprepolymers typically having a molecular weight of from 200 to about4000 can be prepared by reacting an excess of an isocyanate componentwith a polyhydroxy component. The isocyanate component can be adiisocyanate or polyisocyanate as previously described, or can be a lowmolecular weight isocyanate-terminated prepolymer.

The hydroxy component can be one or more of a polyol, polyester,polyether, polycarbonate and R_(f) -glycol, all as described previously.

It can be seen that the properties of ultimate urethane compositions canbe modified by appropriate modifications in the compositions of theprepolymers.

In addition to the formation of the urethane compositions describedabove, the R_(f) -glycols described herein can be converted to thecorresponding bischloroformate by treatment with chlorocarbonylpyridinium chloride: ##STR16## which in turn can be reacted with anappropriate amine to yield a urethane composition: ##STR17## where

A is a divalent organic radical as previously described.

The reaction between the isocyanate component and the hydroxyl componentcan be carried out in bulk, i.e., without solvent, or in the presence ofnon-reactive, anhydrous, organic solvents. Solvent media in which thereaction can be carried out include ketones, such as acetone, methylether ketone and methyl isobutyl ketone; esters such as ethyl acetate,isopropyl acetate, butyl acetate, 2-ethylhexyl acetate; hydrocarbonssuch as hexane, heptane, octane and higher homologs, cyclohexane,benzene, toluene, xylene or blends of aliphatic, cycloaliphatic andaromatic hydrocarbons or aprotic solvents such as N-methylpyrrolidine;it is also possible to employ ethers, both aliphatic and alicyclicincluding di-n-propyl ether, di-butyl ether, tetrahydrofuran and thediethers of polyalkylene oxides. In addition, chlorinated solvents suchas 1,1,1-tri-chloroethane, dichloroethyl ether, ethylene dichloride,perchloroethylene and carbon tetrachloride can be used.

Among the solvents listed, the water miscible solvents such as acetoneand methyl ethyl ketone are most important since they allow conversionsof R_(f) -urethanes into water soluble R_(f) -urethanes as previouslydescribed.

In all cases, the solvents should be anhydrous to avoid urea formation.

The reaction can, if desired, be catalyzed and those catalystsconventionally employed in the urethane art are useful herein. Usefulcatalysts fall principally in two groups

a. amino compounds and other bases:

triethylamine and other trialkylamines, triethylenediamine,1,4-diaza-2,2,2-bicyclooctane, N-(lower)alkylmorpholines,N,N,N',N'-tetra-methylethylenediamine,N,N,N',N'-tetramethyl-1,3-butanediamine, substituted piperazines,dialkylalkanolamines, benzyltrimethylammonium chloride and

b. organometallic and inorganic compounds:

cobalt naphthenate, stannous chloride, stannous octoate, stannousoleate, dimethyl tin dichloride, di-n-butyltin dilaurylmercaptide,tetra-n-butyl-tin, trimethyl-tin hydroxide, di-n-butyltin dilaurate.

Such catalysts may be used singly or in combination with each other.Beneficial synergistic catalysis may occur when combinations are used.

While it is possible to carry out the reaction without the use of acatalyst, it is preferable for reasons of economy and to assure acomplete reaction, to utilize one or more catalysts as listed in amountsranging from 0.001 to 1% based on the weight of the reactants. It issimilarly advantageous to carry out the urethane synthesis at elevatedtemperature, usually between room temperature and 120° C. and preferablyat 60° C. to 80° C. to obtain a complete reaction between 0.5 to 8 hoursreaction time.

The reaction can be easily followed by titration of the isocyanate groupor by IR analysis.

The determination of the critical surface tension in dynes percentimeter shows that the free surface energy of a polyurethane islowered if the novel R_(f) -glycols are incorporated into the urethanechain.

The critical surface tensions are determined by contact anglemeasurements as described by W. Zisman, Contact Angles, Advances inChemistry, No. 43, ACS Publications, Washington, D.C., 1964.

The usefulness of the polyurethane compositions is, conveniently shownby measuring the oil, water and soil repellency ratings of substratessuch as fabrics, paper, leather, etc. which are treated with solutionsor emulsions of the novel urethane compositions.

As already indicated, the urethane compositions of the invention arehighly effective for imparting oil and water repellent properties tosubstrates to which they are applied and coatings of these polymers maybe prepared by any of the well-known techniques. When prepared by bulkor suspension polymerization techniques, these urethane compositions canbe applied, for example, from a dilute solution in suitable a solventsuch as the fluoroalkanes, fluorochloroalkanes, fluoroalkanoic acids,chlorinated alkanes or aromatics, hydrocarbon aromatics, ketones, esterand others. Concentrations of the fluorinated polymer in the solvent canbe adjusted to provide an amount of urethane composition deposited onthe substrate sufficient to provide oil and water repellency. Thisamounts typically to a deposit of from 0.01 to 10%, preferably from 0.1to 1%, of urethane composition, based on the weight of substrate. If theurethane composition is obtained as an aqueous latex or emulsion, thesystem can be diluted with water or other appropriate diluent tosimilarly provide an amount of urethane ranging from 0.01 to 10% of theweight of substrate deposited thereon.

The urethane solution or latex may be applied by any of the knowntechniques such as by dipping, spraying, brushing, padding, roll coatingor by any desired combination of such techniques. The optimum method ofapplication will depend principally on the type of substrate beingcoated.

Coatings of the urethane compositions of the invention may be applied toany desired substrate, porous or non-porous. They are particularlysuited for application to porous materials such as textiles, leather,paper, wood, masonry, unglazed porcelain and the like to providevaluable oil and water repellency properties. However, they may also beapplied to non-porous materials such as metals, plastics, glass, paintedsurfaces and the like to provide similar oil and water repellencyproperties. More specifically the urethane compositions of the inventionact as levelling, wetting and spreading agents in formulations designedfor application to floors, furniture and automobiles. In suchapplications a protective oil and water repellent film is left on thetreated object after the removal of the bulk of the material. Suchlevelling, wetting, spreading and film forming properties are alsouseful in

a. formulations for cleaning glass and other hard, nonporous materials.

b. hair care products such as rinses, shampoos and hair sprays.

c. paint, stain and varnish formulations for application to wood,masonry and ceramics.

In the treatment of paper the urethane compositions may be present as aningredient in a wax, starch, casein, elastomer, or wet strength resinformulation. Aqueous emulsions of the urethane compositions areespecially useful in the treatment of paper. By mixing the urethanecompositions in an aqueous or oil type paint formulation, it may beapplied effectively to unpainted asbestos siding, wood, metal andmasonry. In the treatment of floors and tile surfaces and likesubstrates, and urethane compositions may be applied by theirincorporation in an emulsion or solution.

Because of the ability of the surfaces treated with these urethanecompositions to withstand abrasive action, the advantages incident tothe repellency to oil and water and their resistance to soiling impartedby coating them with the urethane compositions of this invention,preferred classes of articles to be treated are papers and textiles.Illustrative papers are carbonizing tissue, wallpaper, asphaltlaminates, liner board, cardboard and papers derived from syntheticfibers.

For application to textile materials such as fabrics woven andnon-woven, fibers, films, yarns, cut staple, thread etc. or articlesmade from fabrics, fibers, films, yarns, etc. the urethane compositionsof the invention are preferably prepared as aqueous latices or emulsionswhich are then diluted, preferably with water and applied to thetextiles from pad baths which may contain other treating materials. Inaccordance with this technique, the fabric or the textile material ispassed through the bath, passed through squeeze rolls adjusted to leavethe desired amount of the latex on the fabric, dried at a temperature ofabout 25° C. to 125° C. and then cured in a curing oven at a temperaturein the range of from 120° C. to 195° C. for 0.2 to 20 minutes. Theweight of urethane composition deposited on the fabric may range from0.01 to 10% of the weight of fabric. Preferably, very small amounts areused in the range of 0.1 to 1%, often from 0.1 to 0.5% to give highdegrees of water and oil repellency. Any types of textile materials,such as cotton, wool, fiber glass, silk, regenerated cellulose,cellulose esters, cellulose ethers, polyesters, polyamides, polyolefins,polyacrylonitrile, polyacrylic esters, inorganic fibers, etc. eitheralong or blended in any combination may be successfully coated with theurethane compositions of the invention. The resulting textile materialwill be found to be repellent to water and oil, and the textile materialwill retain its resistance to such agents even after many launderingsand dry cleanings.

It will be often advantageous to use the urethane compositions of theinvention in combination with conventional finishes, such as mildewpreventatives, moth resisting agents, crease resistant resins,lubricants, softeners, fat liquors, sizes, flame retardants, antistaticagents, dye fixatives and water repellents.

TEST METHODS

The AATCC water spray test rating was determined according to StandardTest method 22-1985 of the American Association of Textile Chemists andColorists, Volume 61, 1986 (also designated ASTM-D-583-58). Ratings aregiven from 0 (minimum) to 100 (maximum).

The AATCC Oil Rating was determined according to Standard Test method118-1983 of the American Association of Textile Chemists and Colorists.Ratings are given from 0 (minimum) to 8 (maximum). A commonly acceptedlevel of repellency for oil repellent fabrics in the United States is anoil repellency of 4.

All mentioned AATCC Tests are listed in the Technical manual of theAmerican Association of Textile Chemists and Colorists, volume 61,edition 1986.

Polymers prepared in water or a water-solvent mixture or a solvent whichis water-miscible may be applied to polyester-cotton twill by paddingfrom an aqueous pad bath containing also the following permanent pressresins, catalyst and additives (so-called permanent press recipe):

After the padding, the fabric is dried at 100° C. for 2 minutes andcured at 163° C. for 5 minutes.

The invention described above is illustrated by the following examples:

Examples 1 to 24 illustrate the preparation of the R_(f) -glycols.

Example 25 demonstrates the thermal superiority of the subject diols.

Examples 26 to 29 illustrate the preparation of polymeric compositions,and certain utilities of these compositions.

EXAMPLE 1 (C₆ F₁₃ CH₂ CH₂ SCH₂)₂ --C--(CH₂ OH)₂

1,1,2,2-Tetrahydroperfluorooctanethiol (176.7 gm, 0.465 mol) anddibromoneopentyl glycol (60.8 gm, 0.232 mol) are reacted under nitrogenwith potassium carbonate (64.3 gm, 0.465 mol) and 2-pentanone (53.2 gm)as the solvent. The reaction is carried out at 105° C. for 16 hours. Theproduct is stirred at 70° C. and washed once with 350 ml distilledwater. Residual water is removed as an azeotrope and the remainingsolvent is evaporated under house vacuum. The diol (187.5 gm, 94% oftheory) is of 89% purity by GLC. The crude product is recrystallizedtwice from 500 gm toluene to give a final product 95% pure by GLC, m.p.71.5°-73.5° C. Analysis for C₂₁ H₁₈ F₂₆ O₂ S₂ :

Calculated: C, 29.3; H, 2.1; F, 57.4; S, 7.5.

Found: C, 29.4; H, 2.0; F, 56.6; S, 7.7.

EXAMPLE 2 (C₈ F₁₇ CH₂ CH₂ SCH₂)₂ --C--(CH₂ OH)₂

1,1,2,2-Tetrahydroperfluorooctanethiol (111.6 gm, 0.232 mol) anddibromoneopentyl glycol (30.4 gm, 0.116 mol) are reacted under nitrogenwith potassium carbonate (32.1 gm, 0.232 mol) and 2-pentanone (30.7 gm)as the solvent. The reaction is carried out at 100° C. for 17 hours andthe by-product salts (KBr) is removed by a hot gravity filtration. Thecrude product is crystallized and vacuum filtered giving 101.1 gm (82%of theory) of a pale yellow solid, 77% pure by GLC. The diol isrecrystallized twice from toluene (400 g) and once from carbontetrachloride (400 g) to give a final product of 96% purity, m.p.90°-92.5° C. Analysis for C₂₅ H₁₈ F₃₄ O₂ S₂ :

Calculated: C, 28.3; H, 1.7; F, 60.9; S, 6.1.

Found: C, 28.3; H, 1.9; F, 60.9; S, 6.5.

EXAMPLE 2a ##STR18##

This prior art diol is prepared according to Example 2b of U.S. Pat. No.3,935,277.

EXAMPLE 3 ##STR19##

N-[2-Mercaptoethyl]-perfluoro-octanamide (45.3 gm, 0.10 mol) anddibromoneopentyl glycol (12.5 gm, 0.048 mol) are reacted under nitrogenwith potassium carbonate (13.2 gm, 0.10 mol) and 2-pentanone (14.0 gm)as the solvent. The reaction is run at 103° C. for 19.5 hours. Thereaction mixture is stirred at 75° C. and washed twice with 80 gdistilled water. The solvent is evaporated below 115° C. to yield abrown product which is transferred as a brittle solid. This solid isrecrystallized from toluene and then from ethanol to yield a white solid(32 gm, 64% of theory) which is 93% pure by GLC. NMR showed protonresonances at 2.72 ppm, 4 protons, S--CH₂ C: 2.79 ppm, 4 protons, CH₂SCH₂ ; CH₂ SCH₂ C; 3.60 ppm, 4 protons, NH--CH₂ ; 3.65 ppm, 4 protons,CH₂ --OH; 6.97 ppm, 1 proton, N--H.

Analysis for C₂₅ H₂₀ F₃₀ N₂ O₄ S₂ :

Calculated: C, 28.7; H, 1.9; N, 2.7; F, 54.5; S, 6.1.

Found: C, 28.5; H, 1.7; N, 2.8; F, 54.6; S, 6.3.

EXAMPLE 4 ##STR20##

1-Heptafluoroisopropoxy-1,1,2,2-tetrahydroperfluoroalkanethiol(consisting of 73% n=3 homolog and 27% n=4 homolog) (46.0 gm, 0.080 mol)and dibromoneopentyl glycol (10.5 gm, 0.040 mol) are reacted undernitrogen with potassium carbonate (11.1 gm, 0.080 mol) and 2-pentanone(13.0 gm) as the solvent. The reaction is carried out at 103° C. for 18hours. The reaction mixture is stirred at 75° C. and washed twice with80 gms distilled water. The solvent is evaporated below 115° C. to yielda yellow oil which solidifies upon cooling to a waxy yellow gel (32.3gm, 64% of theory). The product is 87% pure by GLC. NMR confirmedstructure with the general proton assignments are the same as in example1.

Analysis for product (n=3, 4):

Calculated: C, 28.1; H, 2.0; F, 55.9; S, 7.0.

Found: C, 27.7; H, 1.6; F, 59.5; S, 5.3.

EXAMPLE 5 ##STR21##

4-Heptafluoroisopropoxy-1,1,2,2-tetrahydroperfluorobutanethiol (43.7 gm,0.13 mol) and dibromoneopentyl glycol (16.5 gm, 0.06 mol) are reactedunder nitrogen with potassium carbonate (17.4 gm, 0.13 mol) and2-pentanone (15.0 gm) as the solvent. The reaction is carried out at103° C. for 19 hours. The product is stirred at 75° C. and washed twicewith 80 ml. distilled water. The solvent is evaporated below 115° C. andthe product transferred hot as a yellow oil which remains fluid. Thediol (31.4 gm, 63% of theory) is of 87% purity by GLC. NMR showed protonresonances at 2.01 ppm, 2 protons,--OH;2.1-3.0 ppm, 8 protons, CF₂ CH₂CH₂ S; 2.70 ppm, 4 protons, SCH₂ C; 3.66 ppm, 4 protons--(CH₂ --OH)₂.

Analysis for product C₁₉ H₁₈ F₂₂ O₄ S₂ :

Calculated: C, 28.8; H, 2.3; F, 52.7; S, 8.1.

Found: C, 28.9; H, 2.4; F, 50.4; S, 7.6.

EXAMPLE 6Tetrakis-(1,1,2,2-tetrahydroperfluoroalkanethio)dipentaerythritol##STR22##

1,1,2,2,-Tetrahydroperfluoroalkanethiol* (139.6 g, 0.28 mol) andsym-tetrabromodipentaerythritol (35.0 g, 0.07 mol) are reacted undernitrogen with potassium carbonate (38.7 g, 0.28 mol) and 2-pentanone(60.0 g) as the solvent. The reaction is run at 103°C. for 19.5 hours,and is then allowed to cool and washed twice with 160 g distilled waterat 75° C. The water layer is removed and the remaining water/2-pentanonemixture azeotroped below 115° C. The product is isolated as a brittle,yellowish-brown solid and crystallized from toluene to yield a paleyellow solid (127.4 g, 86% of theory) m.p. 79.7°-87.4° C.

NMR shows proton resonances at 1.93 ppm, 2 protons, O--H; 2.40 ppm, 8protons, R_(f) --CH₂ --; 2.63-2.90 ppm, 16 protons, CH₂ --S--CH₂ ; 3.43ppm, 4 protons, CH₂ --O--CH₂ ; 3.65 ppm, 4 protons, CH₂ --OH.

Analysis for % OH:

Calculated=1.58%.

Found=1.56%.

EXAMPLE 7 ##STR23##2,2-Bis(1,1,2,2,-tetrahydroperfluorodecylsulfonylmethylene)-1,3-propanediol

2,2-Bis-(1,1,2,2-tetrahydroperfluorodecylthiomethylene)-1,3-propanediol(25.0 g, 0.024 mol) is dissolved in glacial acetic acid (38.09 g, 0.63mol) and warmed to 40° C. Hydrogen peroxide (5.4 gm, 30%) is added andthe mixture is stirred for 1 hour. The reaction mixture is then heatedto 100° C. and additional hydrogen peroxide (10.6 g, 30%) is added. Theproduct precipitates as a yellowish-white solid (24.6 g, 95% of theory)and is crystallized from isopropyl acetate to yield a white solid,m.p.165°-168° C. which was 92% pure by GLC. NMR shows proton resonanceat 2.82 ppm, 4 protons, CF2--CH₂ ; 3.63 ppm, 4 protons, CH₂ ;--SO₂ --CH₂: 3.93 ppm, 4 protons, SO₂ --CH₂ --C ;4.25 ppm, 4 protons, --C--CH₂ OH.

Analysis for C₂₅ H₁₈ F₃₄ O₆ S₂ ;

Calculated: C, 26.70; H, 1.6; F, 57.44; S, 5.70.

Found: C, 26.60; H, 1.5; F, 54.50; S, 6.30.

EXAMPLE 8 Reaction Products of (R_(f) CH₂ CH₂ SCH₂)₂ --C--(CH₂ OH)₂ andγ-Caprolactone

2,2-Bis(1,1,2,2-tetrahydroperfluoroalkanethiomethylene)-1,3-propanediol*(108.5g, 0.10 mol) and S-caprolactone (45.7 g, 0.40 mol) are reacted undernitrogen at 75° C. for 1.5 hours in the presence of a catalytic amountof stannous octanoate. The reaction is then completed at 140° C. for 3hours. The product is a soft waxy yellow solid of mp 28°-34° C.Comparative gel permeation chromatography (styrogel column, THF mobilephase) of the starting material and the product shows an increase in theweight average molecular weight from 1091 to 2508.

EXAMPLE 9 (R_(f) CH₂ CH₂ SCH₂)₂ C(CH₂ OH)₂

1,1,2,2-Tetrahydroperfluoroalkanethiol* (215.8 g, 0.47 mmol) anddibromoneopentyl glycol (60.78 g, 0.23 mmol) are reacted under nitrogenwith potassium carbonate (64.3 g, 0.465 mmol) and 2-pentanone (54 g) asthe solvent. The reaction is carried out at 105° C. for 17 hours. Theproduct is stirred at 70° C. and washed once with 350 ml distilledwater. Residual water is removed as an azeotrope and the remainingsolvent is evaporated under house vacuum. The diol (228.3 g, 92% oftheory) is of 89% purity by GLC.

EXAMPLE 10

Dibromoneopentyl glycol is reacted with1,1,2,2,-tetrahydroperfluoro-decyl amine in triethylamine as solvent at80°-100° C. The reaction is carried out for 12 hours and the product isworked up by acidification and precipitation into water. The powder iscollected by filtration and dried to yield2,2-Bis-(1,1,2,2,-tetrahydroperfluorodecyliminomethylene-1,3-propanediol.

EXAMPLE 11

1,1,2,2,-Tetrahydroperfluorooctanol (10.9 gm, 0.03 mol),3,3-(bromomethyl)oxetane (3.9 gm, 0.016 mol),potassium hydroxide (1.7gm, 0.03 mol), and 15 gm of diethylene glycol dimethyl ether are reactedin the presence of approximately 1.0 gm of 18 Crown-6 in a 50 ml flaskwith gentle stirring for 72 hours at room temperature. Analysis by gaschromatography indicated that the solution contains 36% monoadduct, 64%diadduct. 2.5 gm of solids are filter off and gc/ms identificationconfirms the presence of the desired3,3-(1,1,2,2-tetrahydroperfluorooctyloxy)oxetane and3-(1,1,2,2,-tetrahydroperfluorooctyloxy)-3-bromooxetane.

Identification is made by GC/MS (E.I. Mode) after derivatization withN,O-bis-(trimethylsilyl)-trifluoroacetamide. Two major components areobserved:

Diadduct

MS: m/z 810 absent,780 (M--CH₂ O), 417 b.p., (M--C₆ F₁₃ CH₂ CH₂ O), 403(M--C₆ F₁₃ CH₂ CH₂ OCH₂).

MS (CI) 811 (M+1)⁺

Monoadduct

MS: m/z 526 absent, 447 (M--Br), 417 b.p.(M--CH₂ OBr).

MS (CI) 527 (M+1)⁺

EXAMPLE 12

In a similar fashion to the previous example,1,1,2,2-tetrahydro-perfluorodecanol is reacted at 100° C. for 2-3 hoursto give a mixture of monoadduct-40% and diadduct-60%.

EXAMPLE 13

The hydrolysis of the mixture of mono- and di- C₆ F₁₃ CH₂ CH₂ O-oxetanesobtained in Example 11 is accomplished by reacting the solution of thesubject oxetanes in diethylene glycol dimethyl ether with 10 gm watercontaining 1 gm concentrated sulfuric acid, at reflux for 48 hours. Theproduct separates into two layers and the bottom layer is separated offand washed once with dilute potassium carbonate and twice with water.Evaporation of 10 grams of product at 220° C./1 mm Hg with a Kugelruhraffords 8 grams of an oil. By gas chromatography the product contains79% mono- and 21% diadduct diols, as well as a considerable amount ofbyproducts derived from the solvent.

Diadduct

MS (C.I.)=29 (M+H)⁺

MS (E.I)=m/z 828 (absent), 417 b.p.(C₁₂ H₁₀ OF₁₃), 403 (C₁₁ H₈ O₁₃).

Monoadduct

MS (C.I.)=545(M+H)⁺

MS (E.I.)=m/z 544 (absent), 447 (--H₂ O,Br), 429 (--2H₂ O,Br), 417(--CH₂ O, Br, H₂ O), 71 b.p.(C₄ H₇ O).

EXAMPLE 14

A mixture of C₈ F₁₇ SO₂ N(C₂ H₅)H (20.0 g, 0.047 mol), 87% potassiumhydroxide (3.0 g, 0.047 mol), diglyme (60.0 g) and 18-Crown-6 ether (0.1g) is heated under nitrogen at 100°-105° C. for 30 minutes. The3,3-bis-(bromomethyl)-oxetane (5.7 g, 0.0236 mol) is then added and theentire reaction mass is heated at 100° C. for 13 hours. The salts areremoved upon filtration. Diglyme is removed at 80° C. under vacuum.Proton NMR shows the presence of I in the product. ##STR24## The oxetaneof I can be opened to yield the diol II, ##STR25## according to theprocedure described in example 13.

EXAMPLES 15 to 24

Using the methods described and by techniques similar to Examples 1-14,the following additional sulfido- and sulfone diols are prepared.

    ______________________________________                                                               Perfluoroalkyl Terminated                              Ex.  Thiol             Neopentyl Glycol                                       ______________________________________                                        15   CF.sub.3 CF.sub.2 CH.sub.2 SH                                                                   (CF.sub.3 CF.sub.2 CH.sub.2 SCH.sub.2).sub.2 C                                (CH.sub.2 OH).sub.2                                    16   C.sub.6 F.sub.13 (CH.sub.2).sub.4 SH                                                            (C.sub.6 F.sub.13 (CH.sub.2).sub.4 SO.sub.2                                   CH.sub.2).sub.2 C                                                             (CH.sub.2 OH).sub.2                                    17   C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 CH.sub.2 SH                                                  (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 CH.sub.2                                  SCH.sub.2).sub.2 C                                                            (CH.sub.2 OH).sub.2                                    18   C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 N(CH.sub.3)                                                  (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 N(CH.sub.3)CH.s                           ub.2                                                        CH.sub.2 CH.sub.2 CH.sub.2 SH                                                                   CH.sub.2 CH.sub.2 SCH.sub.2).sub.2 C(CH.sub.2                                 OH).sub.2                                              19   C.sub.8 F.sub.17 SO.sub.2 NHCH.sub.2 CH.sub.2 SH                                                (C.sub.8 F.sub.17 SO.sub.2 NHCH.sub.2 CH.sub.2                                SCH.sub.2).sub.2 (CH.sub.2 OH).sub.2                   20   C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SO.sub.2 NHCH.sub.2                                          (C.sub.8 F.sub.17 CH.sub. 2 SO.sub.2 NHCH.sub.2                               CH.sub.2                                                    CH.sub.2 SH       SCH.sub.2).sub.2 C(CH.sub.2 OH).sub.2                  21   C.sub.7 F.sub.15 CONHCH.sub.2 CH.sub.2 SH                                                       (C.sub.7 F.sub.15 CONHCH.sub.2 CH.sub.2                                       SCH.sub.2).sub.2 C(CH.sub.2 OH).sub.2                  22   CF.sub.3 CF.sub.2 CH.sub.2 CH.sub.2 SH                                                          HO[CH.sub.2 C(CH.sub.2 SCH.sub.2 CH.sub.2                                     CF.sub.2 CF.sub.3).sub.2 CH.sub.2 O].sub.2 --H         23   C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SH                                                           HO[CH.sub.2 C(CH.sub.2 SO.sub.2 CH.sub.2                                      CH.sub.2 C.sub.8 F.sub.17).sub.2 CH.sub.2 O].sub.2                            --H                                                    24   Reaction product of (R.sub.f CH.sub.2 CH.sub.2 SCH.sub.2).sub.2               C(CH.sub.2 OH).sub.2                                                          and Gamma-caprolactone                                                   ______________________________________                                    

EXAMPLE 25 Stability Comparisons of Bis-perfluoroalkylthio-Diols

Thermogravimetric analyses are run on the diols of Examples 2, 3, 7, 8,and prior art diol of Example 2a.

The instrument is run at 10° C./minute to either 350° C. or 500° C. with100 ml/min N₂ or in air.

    ______________________________________                                        TGA (Wt. Loss)                                                                Temperature (°C.) of Indicated Weight Loss                             Diol of          Under Nitrogen                                                                              Under Air                                      Example                                                                              DSC (Tm)  Init.  10%   50%  Init.                                                                              10%   50%                             ______________________________________                                        2      79-86     150    251   295  150  237   285                             7      165-168   195    286   328  185  260   309                             8      28-34     150    293   340  150  265   316                             6      79-87     180    315   356  185  285   335                              2a    50-84      50    180   255  --   --    --                              ______________________________________                                    

These results indicate the thermal superiority of the subjectbis-perfluoroalkylthio-neopentyl type diols. Prior artbis-perfluoro-alkylthio-diols have poor thermal stability andappreciably decompose below 180° C. even under nitrogen. The subjectdiols as examplified above all are appreciably stable to greater than280° C. in nitrogen, even to 260° C. in air. The weight loss of the diolof Example 2 is appreciable by TGA because of volatilization, notdecomposition.

EXAMPLE 26

The diol of Example 9 (78.2 g, 0.073 mmol) is predried azeotropicallywith 1,1,1-trichloroethane. It is then reacted with3,3,4-trimethylhexane-1,6-diisocyanate (11.54 g, .055 mol) undernitrogen in the presence of a catalytic amount of stannous octanoate(0.22 g) with 1,1,1-trichloroethane (135 g) as the solvent. The reactionmixture is heated at reflux for one hour at which time the N═C═Oinfrared band at 2270cm⁻¹ is absent. Then, dimer acid diisocyanate (27.7g, 46 mmol) is added along with N-methyldiethanolamine (3.4 g, 28 mmol)and 1,1,1-trichloroethane (46.6 g).

The mixture is kept at reflux for two hours and the reaction is againjudged to be complete by the disappearance of the N═C═O infrared band.Molecular weight can be determined by gel permeation chromatography.

EXAMPLE 27

The diol of Example 6 (30.0 g, 0.014 mol) is predried azeotropicallywith isopropyl acetate and is then reacted with3,3,4-trimethylhexane-1,6-diisocyanate (2.19 g, 0.01 mol) under nitrogenin the presence of a catalytic amount of stannous octanoate (0.084 g)using isopropyl acetate (49.0 g) as the solvent. The reaction mixturewas heated to 80° C. for 30 minutes and completeness of reaction isindicated by the absence of the N═C═O infrared band at 2270 cm⁻¹. Then,dimer acid diisocyanate (10.36 g, 0.017 mol) is added along withN-methyldiethanolamine (1.67 g, 0.014 mol) and isopropyl acetate (18.0g). The mixture was heated to 80° C. for one hour until the reaction isjudged to be complete by the absence of the N═C═O infrared band.Molecular weight can be determined by gel permeation chromatography.

EXAMPLE 28

The diol of Example 6 (30.0 g, 0.014 mmol) is predried azeotropicallywith isopropyl acetate and is then reacted with3,3,4-trimethylhexane-1,6-diisocyanate (1.45 g., 0.007 mmol) undernitrogen in the presence of a catalytic amount of stannous octanoate(0.084 g), using isopropyl acetate (47.0 g) as the solvent. The reactionmixture is heated at 80° C. for 30 minutes and reaction is complete asindicated by the absence of the N═C═O infrared band at 2270 cm⁻¹. Thendimer acid diisocyanate (10.4 g, 17 mmole) is added along withN-methyldiethanolamine (1.25 g, 10 mmole) and isopropyl acetate (17.40g). The mixture is heated at 80° C. for 1 hour and is again judged to becomplete by the absence of the N═C═O infrared band.

EXAMPLE 29

The polyurethanes of Examples 21 and 23 are compared to an identicalformulation prepared from a prior art diol. ##STR26##

This prior art diol is prepared according to Example 2b of to U.S. Pat.No. 3,935,277.

The polyurethane products are applied by pad application with1,1,1-trichloroethane on both 65/35 polyester/cotton poplin and 100%nylon taffeta in such a way that 0.06% F is applied to thepolyester/cotton and 0.04% F to the nylon. The products are evaluatedafter air drying and curing in a hot air oven at>150° C. for 3 minutes.The products prepared from the subject diols have significantly improvedwater repellency over the prior art diol.

    ______________________________________                                                 65/35 polyester/cotton                                                                           100 nylon taffeta                                          at 0.06% F         at 0.04% F                                        Product  Air Dried/Oven Cured                                                                             Air Dried                                         of Example                                                                             AATCC Oil  AATCC Spray AATCC Spray                                   ______________________________________                                        21       --         --          100                                           23       4          100         100                                           2a (prior-art)                                                                         4            80+         80-                                         ______________________________________                                    

What is claimed is:
 1. A linear polyurethane having recurring structuralunits of the formula Ia or IIa: ##STR27## wherein R_(f) is a straight orbranched chain perfluoroalkyl of 1 to 18 carbon atoms or saidperfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms,Eis branched or straight chain alkylene of 1 to 10 carbon atoms or saidalkylene interrupted by one to three groups selected from the groupconsisting of --NR--, --O--, --S--,--SO₂ --, --COO--, --OOC--,--CONR--,--NRCO--, --SO₂ NR--, and --NRSO₂ --, or terminated at theR_(f) end with --CONR-- or --SO₂ NR--, where R_(f) is attached to thecarbon or sulfur atom, and for formula Ia, X is --S--, --O--, --SO₂ --,or --NR--, and for formula IIa, X is --CONR-- or --SO₂ NR--, where R_(f)is attached to the carbon or sulfur atom, and where R is independentlyhydrogen, alkyl of 1 to 6 carbon atoms or hydroxyalkyl of 2 to 6 carbonatoms, and m is 1, 2 or 3, and A is a divalent aliphatic, cycloaliphaticor aromatic group.
 2. A polyurethane according to claim 1 wherein A isalkylene of 2 to 16 carbon atoms, cycloalkylene of 6 to 15 mcarbonatoms, phenylene, naphthylene or said phenylene or said naphthylenesubstituted by one or two alkyl of 1 to 4 carbon atoms, by alkoxy of 1to 4 carbon atoms, by chloro, by bromo or by nitro, or A is a group ofthe formula ##STR28## where D is a direct bond, oxygen, methylene orethylene, and a, a', a" and a'" each independently are hydrogen, alkylof 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chloro or bromo.3. A polyurethane according to claim 1 wherein A is3,3,4-trimethyl-1,16-hexanediyl or1,3,3-trimethyl-alpha,5-hexahydrobenzylene.
 4. A polyurethane accordingto claim 1 where R_(f) is perfluoroalkyl of 2 to 12 carbon atoms orperfluoroalkyl of 2 to 6 carbon atoms substituted by perfluoroalkoxy of2 to 6 carbon atoms, E is alkylene of 2 to 6 carbon atoms, --CONHCH₂ CH₂--, --CH₂ CH₂ N(CH₃)CH₂ CH₂ --,--CH₂ CH₂ SO₂ NHCH₂ CH₂ --, --CH₂ CH₂OCH₂ CH₂ --, or --SO₂ NHCH₂ CH₂ --, X is --S--, SO₂ -- or --O--, and mis 1 or
 2. 5. A linear block copolymer having soil-release propertieswhich contains, based on the total block copolymer,(a) 15-70% by weightof recurring structural units of blocks Ia, IIa or a mixture thereof,(b) 85 to 30% by weight of recurring structural units of block III,wherein the blocks are connected to one another via urea linkages,blocks Ia or IIa having recurring structural units of the formula##STR29## block III having recurring structural units of the formula:##STR30## wherein R_(f) is a straight or branched chain perfluoroalkylof 1 to 18 carbon atoms or said perfluoroalkyl substituted byperfluoroalkoxy of 2 to 6 carbon atoms, E is branched or straight chainalkylene of 1 to 10 carbon atoms or said alkylene interrupted by one tothree groups selected from the group consisting of --NR--, --O--,--S--,--SO₂ --, --COO--, --OOC--, --CONR--,--NRCO--, --SO₂ NR--, and--NRSO₂ --, or terminated at the R_(f) end with --CONR-- or --SO₂ NR--,where R_(f) is attached to the carbon or sulfur atom, and for formulaIa, X is --S--, --O--, --SO₂ --, or --NR--, and for formula IIa, X is--CONR-- or --SO₂ NR--, where R_(f) is attached to the carbon or sulfuratom, and where R is independently hydrogen, alkyl of 1 to 6 carbonatoms or hydroxyalkyl of 2 to 6 carbon atoms, and m is 1, 2 or
 3. A is adivalent aliphatic, cycloaliphatic or aromatic group, R₄ is hydrogen ormethyl, k is 8 to 100, and p and t are integers and are independently 1to
 5. 6. A block copolymer according to claim 5 wherein R_(f) isperfluoroalkyl of 2 to 12 carbon atoms or perfluoroalkyl of 2 to 6carbon atoms substituted by perfluoroalkoxy of 2 to 6 carbon atoms, E isalkylene of 2 to 6 carbon atoms, --CONHCH₂ CH₂ --, --CH₂ CH₂ N(CH₃)CH₂CH₂ --,--CH₂ CH₂ SO₂ NHCH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, or --SO₂ NHCH₂CH₂ 13 , X is --S--, SO₂ -- or --0--, and m is 1 or
 2. 7. A blockcopolymer according to claim 5 wherein A is alkylene of 2 to 16 carbonatoms, cycloalkylene of 6 to 15 carbon atoms, phenylene, naphthylene orsaid phenylene or said naphthylene substituted by one or two alkyl of 1to 4 carbon atoms, by alkoxy of 1 to 4 carbon atoms, by chloro, by bromoor by nitro, or A is a group of the formula ##STR31## where D is adirect bond, oxygen, methylene or ethylene, and a, a', a" and a'" eachindependently is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to4 carbon atoms, chloro or bromo.
 8. A block copolymer according to claim5 wherein A is 3,3,4-trimethyl-1,6-hexanediyl of1,3,3-trimethyl-alpha,5-hexahydrobenzylene.
 9. A linear polyester havingrecurring structural units of the formula Ib or IIb

    --[OCH.sub.2 C(CH.sub.2 X--E--R.sub.f).sub.2 CH.sub.2 O].sub.m --CO--L--CO]--                                            (Ib)

    or

    --[OCH.sub.2 C(CH.sub.2 X--R.sub.f).sub.2 CH.sub.2 O].sub.m --CO--L--CO]--(IIb)

wherein R_(f) is a straight or branched chain perfluoroalkyl of 1 to 18carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2to 6 carbon atoms, E is branched or straight chain alkylene of 1 to 10carbon atoms or said alkylene interrupted by one to three groupsselected from the group consisting of --NR--, --O--, --S--,--SO₂ --,--COO--, --OOC--, --CONR--,--NRCO--, --SO₂ NR--, and --NRSO₂ --, orterminated at the R_(f) end with --CONR-- or --SO₂ NR--, where R_(f) isattached to the carbon or sulfur atom, and for formula Ib, X is --S--,--O--, --SO₂ --, or --NR--, and for formula IIb, X is --CONR-- or --SO₂NR--, where R_(f) is attached to the carbon or sulfur atom, and where Ris independently hydrogen, alkyl of 1 to 6 carbon atoms or hydroxyalkylof 2 to 6 carbon atoms, and m is 1, 2 or
 3. L is a direct bond, astraight or branched chain alkylene of 1 to 34 carbon atoms,cycloalkylene of 6 to 12 carbon atoms, or arylene of 6 to 16 carbonatoms.
 10. A polyester according to claim 9 where R_(f) isperfluoroalkyl of 2 to 12 carbon atoms or perfluoroalkyl of 2 to 6carbon atoms substituted by perfluoroalkoxy of 2 to 6 carbon atoms, E isalkylene of 2 to 6 carbon atoms, --CONHCH₂ CH₂ --, --CH₂ CH₂ N(CH₃)CH₂CH₂ --,--CH₂ CH₂ SO₂ NHCH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, or --SO₂ NHCH₂CH₂ 13 , X is --S--, SO₂ -- or --O--, and m is 1 or
 2. 11. A polyesteraccording to claim 9 wherein L is tetramethylene or o-phenylene.